Exciton Loss Research Articles

Suppressing the Undesirable Energy Loss in Solution‐Processed Hyperfluorescent OLEDs Employing BODIPY‐Based Hybridized Local and Charge‐Transfer Emitter

Hyperfluorescent organic light‐emitting diodes (HF‐OLEDs) approach has made it possible to achieve excellent device performance and color purity with low roll‐off using noble‐metal‐free pure organic emitter. Despite significant progress, the performance of HF‐OLEDs is still unsatisfactory due to the existence of a competitive dexter energy transfer (DET) pathway. In this contribution, two boron dipyrromethene (BODIPY)‐based donor‐acceptor emitters (BDP‐C‐Cz and BDP‐N‐Cz) with hybridized local and charge transfer characteristics (HLCT) are introduced in the HF‐OLED to suppress the exciton loss by dexter mechanism, and a breakthrough performance with low‐efficiency roll‐off (0.3%) even at high brightness (1000 cd m−2) is achieved. It is demonstrated that the energy loss via the DET channel can be suppressed in HF‐OLEDs utilizing the HLCT emitter, as the excitons from the dark triplet state of such emitters are funneled to its emissive singlet state following the hot‐exciton mechanism. The developed HF‐OLED device has realized a good maximum external quantum efficiency (EQE) of 19.25% at brightness of 1000 cd m−2 and maximum luminance over 60 000 cd m−2, with an emission peak at 602 nm and Commission International de L'Eclairage (CIE) coordinates (0.57, 0.41), which is among the best‐achieved results in solution‐processed HF‐OLEDs. This work presents a viable methodology to suppress energy loss and achieve high performance in the HF‐OLEDs.

Thermally activated delayed fluorescence in a mechanically soft charge-transfer complex: role of the locally excited state.

Molecular design for thermally activated delayed fluorescence (TADF) necessitates precise molecular geometric requirements along with definite electronic states to ensure high intersystem crossing (ISC) rate and photoluminescence quantum yield (PLQY). Achieving all these requirements synchronously while maintaining ease of synthesis and scalability is still challenging. To circumvent this, our strategy of combining a crystal engineering approach with basic molecular quantum mechanical principles appears promising. A holistic, non-covalent approach for achieving efficient TADF in crystalline materials with distinct mechanical properties is highlighted here. Charge transfer (CT) co-crystals of two carbazole-derived donors (ETC and DTBC) with an acceptor (TFDCNB) molecule are elaborated as a proof-of-concept. Using temperature-dependent steady-state and time-resolved photoluminescence techniques, we prove the need for a donor-centric triplet state (3LE) to ensure efficient TADF. Such intermediate states guarantee a naturally forbidden, energetically uphill reverse intersystem crossing (RISC) process, which is paramount for effective TADF. A unique single-crystal packing feature with isolated D-A-D trimeric units ensured minimal non-radiative exciton loss, leading to a high PLQY and displaying interesting mechanical plastic bending behaviour. Thus, a comprehensive approach involving a non-covalent strategy to circumvent the conflicting requirements of a small effective singlet-triplet energy offset and a high oscillator strength for efficient TADF emitters is achieved here.

High-efficiency all fluorescence white OLEDs with high color rendering index by manipulating excitons in co-host recombination layers.

All fluorescence white organic light-emitting diodes (WOLEDs) based on thermally activated delayed fluorescence (TADF) emitters are an attractive route to realize highly efficient and high color quality white light sources. However, harvesting triplet excitons in these devices remains a formidable challenge, particularly for WOLEDs involving conventional fluorescent emitters. Herein, we report a universal design strategy based on a co-host system and a cascaded exciton transfer configuration. The co-host system furnishes a broad and charge-balanced exciton generation zone, which simultaneously endows the devices with low efficiency roll-off and good color stability. A yellow TADF layer is put forward as an intermediate sensitizer layer between the blue TADF light-emitting layer (EML) and the red fluorescence EML, which not only constructs an efficient cascaded Förster energy transfer route but also blocks the triplet exciton loss channel through Dexter energy transfer. With the proposed design strategy, three-color all fluorescence WOLEDs reach a maximum external quantum efficiency (EQE) of 22.4% with a remarkable color rendering index (CRI) of 92 and CIE coordinates of (0.37, 0.40). Detailed optical simulation confirms the high exciton utilization efficiency. Finally, by introducing an efficient blue emitter 5Cz-TRZ, a maximum EQE of 30.1% is achieved with CIE coordinates of (0.42, 0.42) and a CRI of 84 at 1000 cd m-2. These outstanding results demonstrate the great potential of all fluorescence WOLEDs in solid-state lighting and display panels.

Triplets with a Twist: Ultrafast Intersystem Crossing in a Series of Electron Acceptor Materials Driven by Conformational Disorder.

Control over the populations of singlet and triplet excitons is key to organic semiconductor technologies. In different contexts, triplets can represent an energy loss pathway that must be managed (i.e., solar cells, light-emitting diodes, and lasers) or provide avenues to improve energy conversion (i.e., photon upconversion and multiplication systems). A key consideration in the interplay of singlet and triplet exciton populations in these systems is the rate of intersystem crossing (ISC). In this work, we design, measure, and model a series of new electron acceptor molecules and analyze them using a combination of ultrafast transient absorption and ultrafast broadband photoluminescence spectroscopies. We demonstrate that intramolecular triplet formation occurs within several hundred picoseconds in solution and is accelerated considerably in the solid state. Importantly, ISC occurs with sufficient rapidity to compete with charge formation in modern organic solar cells, implicating triplets in intrinsic exciton loss channels in addition to charge recombination. Density functional theory calculations reveal that ISC occurs in triplet excited states characterized by local deviations from orbital π-symmetry associated with rotationally flexible thiophene rings. In disordered films, structural distortions, therefore, result in significant increases in spin-orbit coupling, enabling rapid ISC. We demonstrate the generality of this proposal in an oligothiophene model system where ISC is symmetry-forbidden and show that conformational disorder introduced by the formation of a solvent glass accelerates ISC, outweighing the lower temperature and increased viscosity. This proposal sheds light on the factors responsible for facile ISC and provides a simple framework for molecular control over spin states.

Unexpected role of hole and electron blocking interlayers controlling charge carrier injection and transport in TADF based blue organic light-emitting diodes

There has been increasing interest in blue organic light-emitting diodes based on thermally activated delayed fluorescence (TADF). The construction of a fully optimized device architecture is crucial in accordance with developing high-performance materials because highly efficient electroluminescence cannot be realized without balancing both carrier injection and transport with decreasing several exciton loss processes. Thus, the detailed mechanism of carrier injection, transport, and recombination in emitting layers has to be clarified. In this study, various device architectures for a recently emerged blue TADF molecular system based on multiple donors and acceptors were systematically investigated, especially by focusing on the interlayers. This work also aims to offer guidelines for improving device stabilities. Our findings clarify the role of each layer, providing in-depth insight into device design and the selection of proper materials for each constituted layer.

Revealing the Evolution Processes of Excitons on High Energy Level in Anthracene‐Based OLEDs

AbstractIt is well‐known that the electrically generated excitons can perform the spin evolution between high‐lying excited states, providing an efficient way to utilize triplet excitons in organic light‐emitting diodes (OLEDs). Anthracene families offer an opportunity to deeply investigate the processes of triplet excitons on high‐lying excited states in detail. Here, a simplified model is proposed to study the exciton dynamics in anthracene derivatives‐based devices. The mechanism on the processes of high‐energy level intersystem crossing in anthracene derivatives is well revealed by theoretical calculation, transient electroluminescence, transient photoluminescence, and transient absorption spectrum measurements. Besides, doping strategy is proposed to suppress the exciton loss channel for improving the efficiency of devices. The studies establish an in situ method to evaluate the apparent singlet exciton formation ratio in devices due to the exciton evolution between high‐lying excited states and offer some clues to further utilize these triplet excitons, thus improving the efficiency of the resulting fluorescence OLEDs in the future.

High molecular weight polymeric acceptors based on semi-perfluoroalkylated perylene diimides for pseudo-planar heterojunction all-polymer organic solar cells

In this study bulk heterojunction (BHJ) and pseudo-planar heterojunction (PPHJ) organic solar cells (OSCs) were prepared and studied with perylene diimides (PDIs)-based polymeric acceptors P(4CF8CH-PDI-TT) and P(20CH-PDI-TT). The PDI polymers were used in PPHJ all-polymer solar cells for the first time. Its high molecular weight (Mn of 94.8 kDa), high mobility (μe of 8.40 × 10−3 cm2 V−1 s−1), and excellent solubility make semi-perfluoroalkylated polymer P (4CF8CH-PDI-TT) well polymeric acceptor for PPHJ OSCs. A series of measurements including photoluminescence quenching, dependence of light intensity, carrier mobility, atomic force microscopy, transmission electron microscopy, grazing-incidence wide-angle X-ray scattering, and depth analysis X-ray photoelectron spectroscopy were carried out. The results show that PPHJ devices prepared by the layer-by-layer spin-coating method have better charge transport, higher and more balanced carrier mobility, less exciton recombination loss, and more favorable film morphology than BHJ devices. Consequently, the PPHJ OSCs based on P(4CF8CH-PDI-TT) and P(20CH-PDI-TT) gave power conversion efficiencies (PCE) of 3.43% and 3.15%, respectively, which are higher than 1.71% and 1.10% of BHJ OSCs. It demonstrates that semi-perfluoroalkylated strategy is effective for the construction of high-performance polymeric semiconductors with the PDI block.

Efficient Solution‐Processed Red Fluorescent OLEDs Using Diluted Exciplex Host to Reduce Non‐Radiative Loss of Triplet Excitons

AbstractHigh‐performance red fluorescent organic light‐emitting diodes (OLEDs) are fabricated via a diluted exciplex host strategy to suppress non‐radiative triplet exciton loss in the exciplex sensitized fluorescent emitter system. The solution‐processed red fluorescent OLEDs based on the diluted TCTA:PO‐T2T exciplex host demonstrate higher external quantum efficiency (EQE) than the theoretical 5% limit for traditional fluorescent OLEDs. In the TCTA:PO‐T2T exciplex sensitized fluorescent emitter system, the excess content of TCTA is employed relative to PO‐T2T to manipulate the decay process of triplet excitons. A part of TCTA adjacent to PO‐T2T involves forming the exciplex pair that efficiently converts triplet excitons to singlet excitons via reverse intersystem crossing (RISC), while the other TCTA donors act as the host for the exciplex sensitizer and fluorescent emitter, which inhibits both concentration quenching of the exciplex sensitizer and short‐range dexter energy transfer from the exciplex sensitizer to the fluorescent emitter DCJTB without affecting ISC, RISC, and long‐range Föster energy transfer rate significantly. With this strategy, the formed triplet excitons can be converted to singlet excitons with reduced loss contributing to efficient fluorescent emission under electric excitation. The solution‐processed red fluorescent OLEDs achieve an EQE of 8.1%, much higher than 3.5% of the conventional exciplex sensitized OLEDs.

Management of exciton recombination zone and energy loss for 4CzTPN-based organic light-emitting diodes via engineering hosts

The exciton recombination zone and energy loss of organic light-emitting diodes (OLEDs) with thermally activated delayed fluorescence (TADF) emitter 4CzTPN (1, 2, 4, 5-Tetrakis(carbazol-9-yl)-3, 6-dicyanobenzene) as the dopant are explored by engineering hosts. The results demonstrate that the exciton recombination zone is determined by the matching condition between hole and electron mobility of hosts. The shift of the recombination zone from cathode to anode side induces a blue-shift of the electroluminescent spectra. And energy loss can be reduced by well-matched carrier mobility and TADF feature of host as well as lower energy level offset between host and guest. Specifically, the exciplex-co-hosted device delivers the maximum current/power efficiency/external quantum efficiency of 29.06 cd·A−1/28.89 lm·W−1/8.86%, respectively, enhanced by more than 50% than the single-component-hosted devices. This study illuminates that controlling exciton recombination zone and energy loss via engineering hosts is a feasible strategy for developing high performance TADF OLEDs.

Multiplying the efficiency of red thermally activated delayed fluorescence emitter by introducing intramolecular hydrogen bond

As one of the three primary colors, red organic light-emitting diodes (OLEDs) are indispensable in practical applications. However, red emitters are generally subject to severe non-radiative exciton loss due to their narrow energy gap. In this work, three new thermally activated delayed fluorescence (TADF) emitters were developed, namely 4-(acenaphtho[1,2-b]quinoxalin-9-yl)-N,N-diphenylaniline (TPA-AP), 4-(acenaphtho[1,2-b]pyrido[2,3-e]pyrazin-10-yl)-N,N-diphenylaniline (TPA-APy), and 4-(acenaphtho[1,2-b]pyrazino[2,3-e]pyrazin-9-yl)-N,N-diphenylaniline (TPA-APm), employing a series of finely modified acenaphtho[1,2-b]quinoxaline (AP) derivatives as acceptor units. Among three TADF emitters, an intramolecular hydrogen bond is formed between the donor (D) and acceptor (A) units in TPA-APm. Consequently, the overlap of the frontier molecular orbitals (FMOs) of TPA-APm can increase appropriately, and the fluorescence radiative rate (kF) of TPA-APm is nearly twofold than that of TPA-AP and TPA-APy. Furthermore, the non-radiative decay rate (knr) of TPA-APm is less than that of TPA-AP and TPA-APy by an order of magnitude, which is attributed to the improved molecular rigidity caused by intramolecular hydrogen bond. As a result, TPA-APm-based OLEDs achieved a multiplied external quantum efficiency (EQE) of 21.1% with the electroluminescence peak at 590 nm, comparing to only 7.0% and 11.5% for the TPA-AP-based and TPA-APy-based devices, respectively. These results demonstrate appropriate intramolecular hydrogen bond can suppress the influence of non-radiative decay by simultaneously enhancing molecular rigidity and facilitating the fluorescence process, and have great potential in the design of efficient red TADF emitters.

Optimizing Intermolecular Interactions and Energy Level Alignments of Red TADF Emitters for High-Performance Organic Light-Emitting Diodes.

Adequately harvesting all excitons in a single molecule and inhibiting exciton losses caused by intermolecular interactions are two important factors for achieving high efficiencies thermally activated delayed fluorescence (TADF). One potential approach for optimizing these is to tune alignment of various excited state energy levels by using different doping concentrations. Unfortunately, emission efficiencies of most TADF emitters decrease rapidly with concentrations which limits the window for energy level tunning. In this work, by introducing a spiro group to increase steric hindrance of a TADF emitter (BPPXZ) with a phenoxazine and a dibenzo[a,c]phenazine, emission efficiency of the resulting molecule (BPSPXZ) is much less affected by concentration increase. This enables exploitation of the concentration effects to tune energy levels of its excited states for obtaining simultaneously small singlet-triplet energy offset and large spin-orbital coupling, leading to high-efficiency reverse intersystem crossing. With these merits, organic light-emitting diodes (OLEDs) using the BPSPXZ emitter from 5 to 60 wt% doping can all deliver EQE of over 20%. More importantly, record-high EQEs of 33.4% and 15.8% are respectively achieved in the optimized and nondoped conditions. This work proposes a strategy for developing red TADF emitters by optimizing the intermolecular interaction and energy level alignments to facilitate exciton utilization over wide doping concentrations.

Nonradiative Recombination via Charge‐Transfer‐Exciton to Polaron Energy Transfer Limits Photocurrent in Organic Solar Cells

AbstractA recombination and exciton loss mechanism is reported in organic solar cells involving energy transfer between charge transfer (CT) excitons and polarons, impacting photocurrent generation, particularly in the near‐infrared where polaronic transitions typically reside. This process sets a low‐energy cut‐off in the external quantum efficiency spectrum of an excitonic donor/acceptor interface, determined by the low‐energy polaron absorption peak and the CT state reorganization energy. Furthermore, this process explains the deviation from unity and bias dependence of the CT state's internal quantum efficiency at low photon energies. This process is demonstrated in a variety of systems and it is hypothesized that CT state to polaron energy transfer recombination may be responsible for a share of nonradiative recombination in all organic photovoltaics and can explain numerous experimentally observed device trends regarding photocurrent generation and energy losses. Overall, this work enhances the understanding of photophysical processes in organic materials and allows the design of systems that can avoid this recombination pathway.

Halogen-free donor polymers based on dicyanobenzotriazole for additive-free organic solar cells

Two halogen-free donor polymers PCN1 (zigzag-shape backbone) and PCN2 (linear-shape backbone) were constructed with dicyanobenzotriazole as the acceptor (A) block. Their absorption, energy levels, charge transport properties, and applications as donors in organic solar cells (OSCs) were thoroughly investigated. PCN2 with strong absorption at 400–700 nm, maximum extinction coefficient of up to 8.67 × 104 M−1 cm−1, low highest occupied molecular orbital (-5.50 eV), and the high hole mobility (1.42 × 10−3 cm2 V−1 s−1) is an excellent donor polymer. The OSCs based on PCN2:Y6 reached a high PCE of 15.20% without the addition of any additives and any post-treatment, with an open-circuit voltage (Voc) of 0.862 V, which is by far the highest PCE among OSCs with donor polymers based on benzotriazole derivatives, and it is also one of the highest Voc reported for binary OSCs matched to Y6 in halogen-free donor polymers. The measurements of atomic force microscopy, transmission electron microscopy, and grazing-incidence wide-angle X-ray scattering show that PCN2 has a more orderly arrangement and stronger π-π stacking, and the PCN2:Y6 device exhibits better charge transport, higher and more balanced carrier mobility, less exciton recombination loss, suitable phase separation size, which lead to its higher photovoltaic performance.

Phase rearrangement for minimal exciton loss in a quasi-2D perovskite toward efficient deep-blue LEDs via halide post-treatment

With a facile halide and phase modulating approach, deep-blue emissive quasi-2D perovskite films involving fewer intervening 2D phases are realized, for efficient delivery of excitons to light-emitting phases via streamlined energy transfer.

Light-emitting field-effect transistors with EQE over 20% enabled by a dielectric-quantum dots-dielectric sandwich structure

Emerging quantum dots (QDs) based light-emitting field-effect transistors (QLEFETs) could generate light emission with high color purity and provide facile route to tune optoelectronic properties at a low fabrication cost. Considerable efforts have been devoted to designing device structure and to understanding the underlying physics, yet the overall performance of QLEFETs remains low due to the charge/exciton loss at the interface and the large band offset of a QD layer with respect to the adjacent carrier transport layers. Here, we report highly efficient QLEFETs with an external quantum efficiency (EQE) of over 20% by employing a dielectric-QDs-dielectric (DQD) sandwich structure. Such DQD structure is used to control the carrier behavior by modulating energy band alignment, thus shifting the exciton recombination zone into the emissive layer. Also, enhanced radiative recombination is achieved by preventing the exciton loss due to presence of surface traps and the luminescence quenching induced by interfacial charge transfer. The DQD sandwiched design presents a new concept to improve the electroluminescence performance of QLEFETs, which can be transferred to other material systems and hence can facilitate exploitation of QDs in a new type of optoelectronic devices.

Reduction of Electric Current Loss by Aggregation-Induced Molecular Alignment of a Non-Fullerene Acceptor in Organic Photovoltaics.

Y6 is a recently developed non-fullerene electron acceptor (NFA) with dithienothiophen[3.2-b]-pyrrolobenzothiadiazole as the central unit and improves the performance of organic photovoltaics (OPVs) in combination with many electron-donor polymers. Although Y6 has desirable electronic properties for OPVs, the origin of its superiority as an acceptor is unclear. This study empirically investigates why Y6 is an excellent acceptor by comparing Y6 with F8IC, an analogue with a similar electronic structure, in bulk heterojunction (BHJ) OPVs with various electron-acceptor concentrations. The difference in the performance between Y6 and F8IC appears only at high concentrations, suggesting that it originates from the aggregation structures of the NFAs in the BHJs. Electric current loss analysis reveals that the exciton loss and non-geminate recombination are suppressed more strongly in Y6 OPVs than in F8IC OPVs. Variable angle spectroscopic ellipsometry shows that Y6 molecules align in the in-plane direction at high concentrations, contributing to the high charge generation rate via efficient exciton collection.

Sterically Wrapped Multiple Resonance Fluorophors for Suppression of Concentration Quenching and Spectrum Broadening

AbstractMultiple resonance (MR) emitters are promising for highly efficient organic light‐emitting diodes (OLEDs) with narrowband emission; however, they still face intractable challenges with concentration‐caused emission quenching, exciton annihilation, and spectral broadening. In this study, sterically wrapped MR dopants with a fluorescent MR core sandwiched by bulk substituents were developed to address the intractable challenges by reducing intermolecular interactions. Consequently, high photo‐luminance quantum yields of ≥90 % and small full width at half maximums (FWHMs) of ≤25 nm over a wide range of dopant concentrations (1–20 wt %) were recorded. In addition, we demonstrated that the sandwiched MR emitter can effectively suppress Dexter interaction when doped in a thermally activated delayed fluorescence sensitizer, eliminating exciton loss through dopant triplet. Within the above dopant concentration range, the optimal emitter realizes remarkably high maximum external quantum efficiencies of 36.3–37.2 %, identical small FWHMs of 24 nm, and alleviated efficiency roll‐offs in OLEDs.

Sterically Wrapped Multiple Resonance Fluorophors for Suppression of Concentration Quenching and Spectrum Broadening.

Multiple resonance (MR) emitters are promising for highly efficient organic light-emitting diodes (OLEDs) with narrowband emission; however, they still face intractable challenges with concentration-caused emission quenching, exciton annihilation, and spectral broadening. In this study, sterically wrapped MR dopants with a fluorescent MR core sandwiched by bulk substituents were developed to address the intractable challenges by reducing intermolecular interactions. Consequently, high photo-luminance quantum yields of ≥90 % and small full width at half maximums (FWHMs) of ≤25 nm over a wide range of dopant concentrations (1-20 wt %) were recorded. In addition, we demonstrated that the sandwiched MR emitter can effectively suppress Dexter interaction when doped in a thermally activated delayed fluorescence sensitizer, eliminating exciton loss through dopant triplet. Within the above dopant concentration range, the optimal emitter realizes remarkably high maximum external quantum efficiencies of 36.3-37.2 %, identical small FWHMs of 24 nm, and alleviated efficiency roll-offs in OLEDs.

Recycling of Triplets into Singlets for High‐Performance Organic Lasers

AbstractAchieving continuous‐wave (CW) lasing in organic semiconductors is known to be a difficult task because long‐lived triplets quench radiative singlets via singlet–triplet annihilation (STA). To avoid STA and operate organic lasers in CW or long‐pulse photoexcitation, the triplets need to be removed from an organic laser gain medium. However, this triplet removal leads to a loss of excitons. In addition to removing the detrimental triplets, here it is reported a triplet recycling process, which includes triplet scavenging and successive triplet upconversion via triplet–triplet annihilation (TTA) to regenerate emissive singlet excitons in a laser medium. An anthracene derivative of 9‐(1‐naphthalenyl)‐10‐(4‐(2‐naphthalenyl)phenyl)anthracene (NaNaP‐A) and a laser dye of 4,4′‐bis[4‐(diphenylamino)styryl]biphenyl (BDAVBi) are used as the triplet recycling sensitizer and the emitting laser dye, respectively. In this laser system, NaNaP‐A can efficiently scavenge the triplets formed on BDAVBi because the triplet level is deeper for NaNaP‐A than for BDAVBi, and then NaNaP‐A successively recycles the triplets into the BDAVBi's singlet state via TTA. The TTA compensates and overcomes the STA in this laser system. Hence, these laser devices can be operated with long pulse widths of up to 10 ms. This unique triplet recycling behavior is confirmed by transient photoluminescence (PL) and electroluminescence (EL) studies.

Reducing the efficiency roll-off in organic light-emitting diodes at high currents under external magnetic fields

Singlet-polaron and triplet-polaron annihilation mechanisms are the most detrimental exciton quenching processes that lower the efficiency of organic light-emitting diodes (OLEDs) at high current densities, causing so-called efficiency roll-off in these devices. These exciton loss mechanisms are also the critical obstacles towards the realization of electrically pumped organic semiconductor lasers, which require very high current densities to reach threshold. Herein, under a relatively large external magnetic field, we demonstrate that the efficiency roll-off at high current densities in europium (Eu 3 + )-based solution-processed OLEDs can be suppressed to some extent while the luminance is enhanced. We achieve this by reducing the Förster-type exciton–polaron annihilation processes. Under the applied magnetic field, we show that manipulation of the polaron-spin and exciton dynamics lead to a quantitative roll-off suppression. • Modified exciton dynamics under an external magnetic field in lanthanide-based OLEDs. • Efficiency roll-off suppression due to reduced exciton–polaron quenching. • Brightness enhancement under an external magnetic field.